Leuco sulphuric acid esters of the anthraquinone series



Patented Apr. 18, 1944 LEUCO. SULPHURIG ACID ESTERS OF THEANTI-IFLAQUINONE SERIES Eduard Besler, 'Frankfort-on-the-Main, Gern iassignor-to General Aniline & Film Cor- --poration, New York, N. Y., acorporation of Delaware No Drawing. Application April 4, 1941'; SerialNo. 386,771u 'InGermrmy April 13, 1940 3 Claims. I (Cl. 260-193) Thepresent invention relates to leuco sulphuric methyl- -methoxy 4bromanilide, acetoacetic acid esters of the anthraquinone series andmoreacid 2 5 diethoxy 4 b hd acetqac'et ic part a y to p unds f the f l sgene. acid-2.4-dimethoxy 5 bromanilide, acetoacetic eral formula:acid-3-chloro-l-naphthalide, acetoacet'ic acid-4- OSOaNa '5chloro-l-naphthalide, acetoacetic acid-8-chlorol-naphthalide,acetoacetic acid 4.8 -dichloro-l naphthalide, acetoacetic acid 5.8dichlo'io- 1= naphthalide. v In comparison with the dyeings producedwith :10 the dyestuff disclosed in the example of German N soaNa PatentNo. 539,115 the dyeings produced with H the new compounds haveyforinstance, anessenf tially better fastness towashing on artificial silkens-c OCH-CONH-Rhal0gcn staple fi i i The new leuco sulphuric acidesters maybe pre-= pared in a very good yield and in a very pure stateby treating the products obtained by cou pling diazotizedalpha-aminoanthraquinone with halogenated acetoacetic acid arylides inthe pres- 0 ence of a tertiary base, for instance pyridine,

with chlorosulphonic acid or another agent yielding sulphuric anhydridein the presenceof a metal, such as copper, iron or the like Theesterification mass is advantageously worked up 5 by introducing it intoWater and sodium carbonate or caustic soda solution, freeing it from thepyridine by distillation under reduced pressure and from the metal saltsby filtration. From the filtrate the resultant sulphuric acid estersalts are salted out by means of sodium chloride. The precipitatedsodium salts of the leuco sulphuric acid. esters are filtered withsuction wherein R represents a radical of the-benzene or naphthaleneseries.

In German Patent No. 539,115, there is described the leuco sulphuricacid ester of the amdyestuff from diazotized alpha-amino-anthraquinoneand acetoacetic acid anilide. This leuco sulphuric acid ester dissolveseasily-in Water and yields, when dyed or printed on the fiber accordingto the method usual for this class or" dyestuffs, a yellow shade whosefastness propertiesdo not comply with requirements of the practice.

Now, 'I have found that Idyestufis of improved fastness properties areobtained by transforming into the leuco sulphuric acid esters the.azo-dyestufis obtainable from diazotized alpha-amino-- anthraquinoneand acetoacetic acid arylides, halogenat i t c f radlcaly W as, and,after stabilization, dried under reduced instance, acetoaceticac1d-2-chl0raml1de, acetopressura acetic acid-3 a'cetoaicetlc wi "Thefollowing examples serve to illustrate the chloranilide, acetoaceticac1d-.2. 5 -dichloroamlide, invention but they are o intended to limitit acetoacetic acid-2.6-d1'chloraml1de, acetoacetic n thereto, the partsbeing by weight: acid 2.4.5 trichloranihde, acetoacetic acme.- (1) Intothe t -ifi ti mixture obtained methoXy 5 chloralililidei acetoafleticacid f" y causing 40 parts of chlorosulphonic acid tomethoxy-G-chloranihde, acetoa i fil firun into 269 parts of a pyridinefraction boiling methoxyi-chloranilide, acetoacetic ac1d-4.6-dit 125-1260., there is introduced a mixture methOXY 3 Chloranilide, acetoacet-icacid 0f 20 parts of copper powder and 20 parts of the methoxyl-acety m 5chloranilide, 2106mdyestufi obtainable by coupling diazotized alphaacetic acid-2meth0Xy-4-benZoylomin0-5-chloraminoanthraquinone withacetoacetic acid-2- anilide, acetoacetic acid-2-methyl-4-chloranilide, tchloranilide. By stirring the Whole for 1 hour acetoaceticacid-2-methyl-5-chloranilide, acetoat 40 C., the esterification isfinished. The mixacetic acid-3-methyl-6-chloranilide, acetoacetic tureis introduced into ice-water to which 10 acid-2 methyl 4.5dichloranilide, acetoacetic parts of diatomaceous earth have been added.acid2-p acetoacetic acid The P'i -pyridine-comple:r salt whichsepazethoxy -4 bromanilide, acetoacetic acid-2 rates is isolated fromthe supernatant liquor by decanting, stirred with 500 parts of ammoniaof 10% strength, filtered with suction and distilled under reducedpressure with 1000 parts of a sodium carbonate solution of 2% strength,until it is free from pyridine. The solution of the ester is freed fromthe separated copper salts by filtration, and potassium chloride orsodium chloride and 25 parts of ammonia are added. The leuco sulphuricacid ester thus salted out is filtered with suction in the cold andstabilized by addition of a small quantity of sodium carbonate. Itcorresponds to the following formula:

OSOsNa l CHa-C o-oH-c o-NHO By acid oxidation the ester yields insubstance as well as on the fiber a vivid yellow of very good fastnessproperties.

(2) By replacing the dyestuff of Example 1 by the product obtained bycoupling diazotized alpha-aminoanthraquinone with acetoacetic acid-4-chloranilide, the esterification occurs in the same manner.

The leuco sulphuric acid ester obtained is easily soluble in water andyields, when printed according to the method usually applied withdyestufis of this class, a somewhat greenish yellow print of very goodfastness properties.

(3) 200 parts of chlorosulphonic acid are added, drop by drop, at 15C.-20 C. to about 1000 parts of pyridine (fraction boiling at 125 C.126C.) thereupon, 100 parts of copper powder and 100 parts of the dyestuffobtainable from diazotized alpha-amino-anthraquinone and acetoaceticacid-5-c hl o r o-2-amino-1.4-dimethoxy-benzene are introduced. Themixture is stirred for 2 hours at 40 C.; the reaction mass i thenintroduced, while stirring, into 10000 parts or" water and 50 parts ofdiatomaceous earth. The Whole 1 is allowed to stand for some time, untilthe solid matter deposits, and the mixture of pyridine and water ispoured off. The remaining copper-pyridine-complex salt is washed twicewith 5000 parts of water each time and then dissolved in 9000 parts ofwater and 240 parts of caustic soda solution of 40 B. by stirring forhour; the separated copper salt is filtered with suction and Washed.From the filtrate the leuco sulphuric acid ester is salted out by meansof sodium chloride, filtered with suction and the crude ester isdissolved and re-precipitated again.

When developed on cotton in the usual manner with acid oxidizing agents,the leuco sulphuric acid ester yields a vivid orange of very goodfastness properties. I

(4) 150 parts of chlorosulphonic acid are caused to run, while stirringand cooling, into 800 parts of a pyridine fraction boiling at about 125C. to about 126 C. and 100 parts of the dyestuii obtainable by couplingdiazotized alpha-aminoanthraquinone with acetoaceticacid-2-chloranilide, and 60 parts of powdered iron ar introduced. Thereaction mass is heated for a short time to 40 C.-50 C. On account ofthe reaction heat, the temperature rises for a short time to 60 C. Afterstirring for 1 hour, the esterification mixture is poured into 4000parts of water and 230 parts of sodium carbonate, distilled underreduced pressure until it is free from pyridine, freed from theferruginous mud by filtration and the sulphuric acid ester is separatedfrom the filtrate by means of about 15% of sodium chloride. Theprecipitated ester is filtered with suction, washed with a sodiumchloride solution and made into a paste with 2% of sodium carbonate.

The leuco sulphuric acid ester is identical with that prepared accordingto Example 1.

(5) By replacing the dyestufi of Example 4 by the product obtained bycoupling diazotized alpha-aminoanthraquinone with acetoacetic acid-4-chloranilide, a leuco sulphuric acid ester is ob tained which isidentical with the compound prepared according to Example 2.

(6) Into an esterification mixture of 800 parts of a pyridine fractionboiling at C.-126 C. and parts of chlorosulphonic acid, there areintroduced 60 parts of powdered iron and 100 parts of the dyestuffobtainable by coupling diazotized alpha-aminoanthraquinone withacetoacetic acid-5-chloro-2-amino-1.4-dimethoxybenzene. The reactionmixture is heated to 40 C.- 50 C. and, owing to the reaction heat, thetemperature rises for a short time to 60 C. When the esterification isfinished the reaction mass is introduced into 4000 parts of water and230 parts of sodium carbonate and freed from pyridine by distillationunder reduced pressure. The aqueous solution is separated from theferruginous mud by filtration and the sulfuric acid ester formed issalted out from the filtrate by means of sodium chloride. The ester isfiltered with suction and stabilized by means of sodium carbonate. It isidentical with the compound described in Example 3.

By replacing the azo-dyestuffs used in the preceding examples by theproducts obtained by coupling diazotized alpha-amino-anthraquinone withother halogenated acetoacetic acid arylides disclosed in thedescription, leuco sulphuric acid esters are obtained which are easilysoluble in water and yield, when dyed or printed according to the methodusually applied with dyestuffs of this class, yellow to orange tints ofgood fastness properties.

I claim:

1. The leuco sulphuric acid esters'of the anthraquinone seriescorresponding with the following formula:

OSOsNa w SOaNa wherein R represents a member of the group consisting ofradicals of the benzene and naphthalene series, being easily soluble inwater and yielding by acid oxidation in substance and on the fiberyellow to orange shades of good properties of fastness.

2. The leuco sulphuric acid esters of the anthraquinone seriescorresponding with the followthraquinone series corresponding to thefollowing general formula: ing formula: (iJSOaNa i 5 /\l i I OSOsNaSOKNQ OCH, III iilkoxy 10 f 1 ens-c 0-01-1-0 ONHR-l1alogen CHPC O-CEPCwherein R represents a radical of the benzene series, readily soluble inwater and yielding by 15 being easily soluble in water and yielding byacid acid oxidation in substance and on th fiber yeloxidation inSubstance d on the fib r vivid low to orange shades of good propertiesof fastorange shades of very good properties of fast ness.

neSs. 3. The leuco sulphuric acid ester of the an- EDUARD BESLER.

